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and 10) or 40 h (sulfides 7 and 12). The reactions were
then extracted with dichloromethane (4 · 15 mL) and
the organic layers dried over Na2SO4, filtered and evap-
orated under reduced pressure. The crude residues were
purified by flash chromatography on silica gel (petro-
leum ether/ethyl acetate 9:1, except for substrate 12,
petroleum ether/ethyl acetate 8:2) to afford the chiral
sulfoxides: (S)-5a (colourless oil, 26.7 mg, 49% yield),
(S)-7a (colourless oil, 21.6 mg, 39% yield), (R)-10a (col-
ourless oil, 20.8 mg, 38% yield) and (S)-12a (yellow pale
oil, 17.6 mg, 31%).
4. (a) Ozaki, S.-I.; Ortiz de Montellano, P. R. J. Am. Chem.
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5. (a) Colonna, S.; Gaggero, N.; Pasta, P.; Ottolina, G.
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4.3.1. (S)-n-Butyl phenyl sulfoxide, (S)-5a. Determina-
tion of ee by HPLC analysis: Chiralcel OB, petroleum
Torres Pazmino, D. E.; Ottolina, G.; Fraaije, M. W.;
˜
Carrea, G. Tetrahedron: Asymmetry 2005, 16, 3077–
3083.
ether-i-propanol (88:12), 1.0 mL/min, 254 nm, tR 11.9
25
(R) and 19.7 (S) min. ½aꢂD ¼ ꢀ131:5 (c 0.98, acetone)
6. (a) Alphand, V.; Furstoss, R. In Enzyme Catalysis in
Organic Synthesis; Drauz, K., Waldmann, H., Eds.;
Baeyer–Villiger Oxidations; VCH: Weinheim, 1995; pp
ee 71%.
4.3.2. (S)-Allyl phenyl sulfoxide, (S)-7a. Determination
745–772; (b) Mihovilovic, M. D.; Muller, B.; Stanetty, P.
¨
of ee by HPLC analysis: Chiralcel OB, petroleum ether/
Eur. J. Org. Chem. 2002, 3711–3730; (c) Alphand, V.;
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i-propanol (85:15), 1.0 mL/min, 254 nm. tR 13.6 (S) and
25
17.9 (R) min. ½aꢂD ¼ ꢀ164:8 (c 1.08, EtOH) ee 98%.
4.3.3. (R)-Chloromethyl phenyl sulfoxide, (R)-8a.
Determination of ee by HPLC analysis: Chiralcel OD
7. (a) Kamerbeek, N. M.; Moonen, M. J. H.; van der Ven, J.
G. M.; van Berkel, W. J. H.; Fraaije, M. W.; Janssen, D.
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Janssen, D. B. Appl. Environ. Microbiol. 2003, 419–426.
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F. H.; Fraaije, M. W. J. Mol. Catal. B: Enzym. 2005, 32,
135–140.
petroleum
ether/i-propanol
(95:5),
1.0 mL/min,
25
254 nm. tR 14.8 (S) and 17.6 (R) min. ½aꢂD ¼ ꢀ83:3 (c
0.73, acetone) ee 89%. Enantiomeric excess obtained in
the enzymatic reaction 76%.
4.3.4. (R)-Chloroethyl phenyl sulfoxide, (R)-9a. Deter-
mination of ee by HPLC analysis: Chiralcel OD petro-
leum ether/i-propanol (97:3), 1.0 mL/min, 254 nm. tR
25
27.9 (S) and 30.8 (R) min. ½aꢂD ¼ ꢀ101:8 (c 1.39, ace-
tone) ee 98%. Enantiomeric excess measured in the enzy-
matic oxidation 81%.
10. de Gonzalo, G.; Ottolina, G.; Zambianchi, F.; Fraaije, M.
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4.3.5. (R)-Methoxymethyl phenyl sulfoxide, (R)-10a.
Determination of ee by HPLC analysis: Chiralcel OD
petroleum ether/i-propanol (9:1), 1.0 mL/min, 254 nm.
25
tR 11.8 (S) and 14.6 (R) min. ½aꢂD ¼ ꢀ207:1 (c 0.84,
CHCl3) ee 97%.
13. (a) Branchaud, B. P.; Walsh, C. T. J. Am. Chem. Soc.
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4.3.6. (S)-4-Aminophenyl methyl sulfoxide, (S)-
12a. Determination of ee by HPLC analysis: Chiralcel
OD, petroleum ether/i-propanol (75:25), 1.0 mL/min,
25
254 nm. tR 20.3 (R) and 28.8 (S) min. ½aꢂD ¼ ꢀ85:1 (c
15. Holland, H. L.; Brown, F. M.; Larsen, B. G. Bioorg. Med.
Chem. 1994, 2, 647–652.
0.82, EtOH) ee 95%.
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Acknowledgements
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R. W.; Chenchaiah, P. C. Can. J. Chem. 1985, 63, 1118–
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Gaggero, N.; Battistel, E.; Bianchi, D. Tetrahedron:
Asymmetry 1992, 3, 1063–1068; (d) Secundo, F.; Carrea,
G.; Dallavalle, S.; Franzosi, G. Tetrahedron: Asymmetry
1993, 4, 1981–1982; (e) Holland, H. L.; Bornmann, M. J.;
Lakshamaiah, G. J. Mol. Catal. B: Enzym. 1996, 1, 97–
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Sharma, N. D.; Haughey, S. A.; Kennedy, M. A.;
We thank CERC3 for funding. COST D25/0005/03 is
gratefully acknowledged.
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